Alpha-substituted diethoxy-dithiophosphorylacetic esters



2,9416% Patented Aug. 2., 196%) k Q I ALPHA-SUBSTITUTED DIETHOXY DITHIOPHOSR PHORYLACETIC nsrnns Raifaello Fusco, Giuseppe Losco, and Mario Perini, Milan, Italy, assignors to Montecatini, Societa Generale 9]; llndustria Mineraria e Chimica, a corporation of No Drawing. Filed June 6, 1956, Ser. No. 589,587 Claims priority, application Italy June 14, 1955 5 Claims. (Cl. 167-30) The present invention relates. to organic esters of phosphoric acid and to their use as insecticides, rodenticides and, generally, as agents for the control ofparasites endangering plants and buildings, asswell as'to the process for the preparation of these compounds.

In the prior patent'application SerialNo. 545,779 of November 8, 1955, phosphoric esters have'been disclosed; corresponding to the general formula ii 7 R0 S-OH2C0'OR' wherein R represents a lower alkyl, such' as methyl and ethyl, and R represents asaturated straight or branched chain alkyl.

Now we have found that certain modifications of the foregoing compounds have "a decidedly higher. insecticidal power. This is particularly the case with phosphoric esters corresponding to the general formula R0\ s" A no s zn cooa' wherein R is an unsubstituted or substituted aromatic radical, such as phenyl, chlorophenyl, nitrophenyl, naphthyl, andothers.

The products of the present invention-=are prepared by; reacting a phosphate of thegeneral formula wherein Y is an alkali metal, ammonium, or an alkaline. earth metal, with an ester of an alpha-halogen-substituted alpha-arylacetic acid, of the general formula wherein hal represents Cl, Br or I, according to the scheme:

to neutralize the acid, such as .Na CO K CO BaCO NaOH, KOH, NaHCO KHCO etc.

The reaction is carried out in the presence of a solvent for either or both reactants. The following solvents were found to be useful: Water, alcohols, ketones, esters,

dioxanet andaromatic hydrocarbons (benzene, toluene,

xylene) EXAMPLE 1 20 g. diethyldithiophosphoric acid, dissolved in cc. acetone; are neutralized with about 6 g. anhydrous sodium carbonatea The solution is stirredfor half an hour at room temperature. and 25 g; ethyl alph.a-phenyl-alphabromoa'cetate are added. After standing overnight, most of the solvent is slowly distilled off at normal pressure. The residue is cooled and shaken with water and a 5% NaHCO solutionuntil the pH is adjusted to 7. The mixture is'dried over MgSO4 and is then distilled, whereby a fractiorr boiling at about l49-150 C./0.05 mm. Hg is collected. About 20 g. of a straw-colored oil are obtained.

The analysis agrees with the formula (mmOnPsson-o 0 oolHi EXAMPLE 2 11.5 g. diethyldithiophosphoric acid dissolved in 100 cc. acetone are neutralized with 3.3 g. anhydrous sodium carbonate. After stirring for half an hour, 16 g. ethyl alpha-p=nitrophenyl-alpha-bromoacetate, dissolved in 60 cc. acetone, are added drop by drop. The mixture is refluxed for 2 hours and the acetone is distilled 01f. After cooling, the mixture is treated with ice water, extracted with CC],, and the extract shakenwith a 5% NaHCO solution until the pH is adjusted to7. The extract isthendried over MgSO and the solvent removed under-vacuum on a boiling water bath. The residue is a dark red oil.

The analysis agrees withthe formula (C:H50)zPSSCH O O0 01H:

0H4N0r EXAMPLE 3 38 g. crude dimethyldithiophosphoric acid dissolved in cc. acetone are neutralized with 13 g. anhydrous sodium carbonate. After stirring for half an hour, 48.6 g. ethyl alpha-phenyl-alpharbromoacetate are added. The mixture is refluxed for them and most of the acetate is distilled olf at normal pressure on a boiling Water bath. After cooling, the mass istreated with ice water and extracted with carbon tetrachloride. The extract is shaken with a 5% NaHCO solution until the pH is adjusted to 7, dried over MgSO and the solvent removed under vacuum on a boiling water bath. The residue consists of 49 g. of a yellow oil.

figures,- Dgg:l.2635 The analysis agrees with theformula (ommr-rss-omo 0 OCZHG OoHt EXAMPLE 4 3 The analysis agrees with the formula [(CHS)2CHO]2PSSCHCOO02H! EXAMPLE amount of NaHCO and extracted with ether. The ether extract is dried over MgSO and the solvent is distilled off. 32.3 g. of an oil are obtained. The oil is distilled at 0.05 mm. Hg.

B.P.0-05158-160 0.; 11%:15470; Dggzh238l The analysis agrees with the formula:

(OzH O) PSS,CH-C0OC1Hs EXAMPLE 6 23.5 g. isopropyldithiophosphoric acid dissolved in 100 cc. acetone are neutralized with 6.8 g. anhydrous sodium carbonate. 23.2 g. ethyl p-chlorophenyl-alpha-chloroacetate are added. The mixture is refluxed for 2 hours and the acetone is distilled off. After cooling, the mass is poured into 400 g. ice; the oil which separates is extracted with ether and, after the ether extract has neutralized by shaking with a NaI-ICO solution and dried, the ether is evaporated under vacuum on a boiling water bath. The residue, amounting to 37.7 g. is a yellow oil.

20, 20 n .1.5332, 13 41914 The analysis agrees with the formula [(CHahCHOhPSS-CH-COO01H EXAMPLE 7 27 g. diethyldithiophosphoric acid dissolved in 150 cc. ethyl alcohol are neutralized with 8 g. anhydrous sodium carbonate. The solution is stirred for half an hour, filtered and treated with 33 g. isopropyl alpha-bromoalpha-phenylacetate. After standing overnight, the mixture is refluxed for 2 hours and taken up with Water. The oil which separates is shaken with NaHCO solution until it has a pH of 7. During this treatment, the

oil solidifies almost completely. The mixture is filtered EXAMPLE 8 29 g. crude dimethyldithiophosphoric acid dissolved in 150 cc. dioxane are neutralized with 10 g. anhydrous sodium carbonate. The mixture is stirred for half an hour and 37.5 g. methyl alpha-bromo-alpha-phenylacetate are added. The mass is heated to -80 C. for 2 hours. After standing overnight, NaCl that had formed is filtered ofit and the filtrate is diluted with water. The oil which separates is dried over MgSO 40 g. of a straw-colored oil are obtained. Upon distilling at 0.1 5 mm. Hg, this oil yields of a product having a B.P. of 161 C.

. The distilled product shows n .1. 5631, D .l. 2656 The analysis agrees with the formula (OHaO)zPSSCH0OOCHa EXAMPLE 9 I 9.5 g. diisopropyldithiophosphoric acid dissolved in 50 cc. acetone are neutralized with 2.4 g. anhydrous sodium carbonate. Undissolved sodium carbonate is separated by decanting and -10 g. of ethyl alpha-chloro-alphanaphthylacetate are added to the solution. Sodium chloride separates slowly. The mixture is refluxed for 2 hours. The solvent is distilled off, ice water is added and the mixture is extracted with ether. The ether extract is neutralized with sodium carbonate, shaken with water and dried over anhydrous magnesium sulphate. The solvent is evaporated under vacuum on a boiling water bath. 14.6 g. of a dense, reddish oil remain.

The analysis agrees with the formula (olmohrsson-wooolm Evaluation of the biological activity of products of the foregoing examples Compounds covered by the herein-claimed general formula have shown to possess valuable biological properties that render them useful in parasite control.

The following examples are presented to illustrate these properties.

M usca domestica Upon topical application, by means of a micro-syringe, of acetone solutions of the products under examination, to five days old flies, the following average percent mortalities were observed.

TABLE I 'y/fiy 50 10 2 0.4

Example Percent mortality after 20 hours Ethyl alpha (0,0 diethyldithio phosphorybphenylacetate 1 Ethyl alpha (0,0-diethy1dlthio phosphoryl)4 nitrophenylace mm 100 96 2 Ethyl alpha (0,0 dimethyldlthi ophosphoryl)phenylacetate 100 100 3 Ethyl alpha (0,0 dllsopropyldi thlophosphoryl)phenylaeetate... 100 100 0 4 Ethyl alpha (0,0 dlethyldlthio plzosphorylM-chlorophenyl acee- 100 5 Isopropyl alpha (0,0 dlethyl dithiophosphoryl)pheny 100 7 Methyl alpha (0,0 dimethyl dithiophosphoryl)phenylacetate. 100 91 8 Ethyl alpha (0,0 dlisopropyl dlthiophosphory1)naphthyl acetate 17 1 0 9 As a result of tarsal absorption, by introducing five days old female flies into beakers previously treated with controlled amounts of benzene solutions of the active substances under examination, and leaving the flies in contact with these substances for 20 hours, the following mortalities were observed:

. TABLE II Example Percent mortality 1 after 20 hours Ethyl alpha (0,0 diethyldithio phosphoryDphenylacetate. 100 1 Ethyl alpha (0,0 diethyldithlo phosphoryl)3 nltrophenyl ace tate-. 100 2 Ethyl alpha (0,0 dimethyldithio phosphoryDphenylacetate 100 3 yl alpha (0,0 diisopropyl dithiophosphoryl)phenylacetate 45 100 4 Ethyl alpha (0,0 diethyldithio phosphoryl)4 chlorophenyl acetate 99 100 5 Isopropyl alpha (0,0 dlethyldi thiophosphoryl)phenylacetate 100 7 Methyl alpha (0,0 dimethyldi thiophosphoryl)phenylacetate 100 8 Eth alpha (0,0 dilsopropyldi thlophosphoryl)naphthylacetate- 0 9 97 9 A plus fabae Upon spraying a population of aphides, apterous virginoparous females, on bean plants under standardized conditions with suitably formulated aqueous dispersions of the compounds under examination, the following average mortalities were observed:

TABLE III conc. inpercent 0.5 0.1 0.02

Example Percent mortality after 24 hours Ethyl alpha-(0,0 dlethyldithlophos phoryDphenylacetate 100 1 Ethyl alpha (0,0 diethyldithiophos phoryl)4 -nitrophenyl acetate 98 6O 10 2 thyl alpha (0,0 dimethyldithiophos phoryDphenylacetate 100 97 60 3 Ethyl alpha (0,0 diisopropyldithio phosphoryDphenylacetate 45 15 0 4 Ethyl alpha (0,0 diethyldithiophos phoryD i chloropheuyl acetate. 100 90 10 5 Isopropyl alpha (0,0 diethyldi phosphoryl)phenylacetate- 100 7 Methyl alpha (0,0 dimeth phosphoryl) phenylacet ate- 100 92 20 8 thyl alpha (0,0 diisopropyldith phosphoryl)naphthylacetate 16 3 0 9 Tetrzmichus telarizrs Upon spraying a mixed population of mites at various stages of growth on bean plants under standardized conditions with suitably formulated aqueous dispersions of the substances under examination, the following average mortalities were obtained:

TABLE IV conc.lnpercent 0.5 0.1 0.02

Example Percent mortality after 24 hours Ethyl alpha-(0,0-diethyldithiophosphoryl)phenylacetate Ethyl alpha-(0,0-diethyldithiophosphoryl)4-nitrophenyl acetate Ethyl alpha-(0,0-dimethyldithiophosphoryl)phenylacetate Ethyl alpha-(0,0-d.iisopropyldithiophosphoryDphenylacetate Ethyl alpha-(0,0-diethyldithiophosphoryl)4-chlorophenyl acetate Isopropyl alpha-(0,0-diethyldithiophosphoryDphenylacetate. Methyl al o H co @(DNCHWKWMH Spraying of mite eggs gave the average mortalities indicated in Table V:

LD 50 and LD 95, expressed in diflerent measuring units, were determined by the same technique for the various applications. The results are listed in Table VI.

The herein claimed compounds may be used as such as insecticides or fungicides, or one or several of them may be admixed with other known pesticides, such as insecticides and/or fungicides and applied as solids or in form of solutions or dispersions in inert vehicles. Moreover, these compounds may be employed in conjunction with Plant nutrients and fertilizers.

TABLE VI Musca domestica A. fabae T. telartus T. telariua eggs Formula Example topical tarsal LD in L1) 95 in LB 95 in LD 50 in LD 50 in percent percent percent w/fly gJm.

Ethyl alpha-(0,0- ethyldithiophose phoryl) phenylacetate 0. 002 0.00038 0.02 0.0005 0.17 1 Ethyl alpha(0,0-diethyldith1ophosphoryIMnitrophenyl acetate- 0. 22 0. 0024 0. 20 0. 0015 0. 14 2 thy pha-(0,0-dimethyld.lthi phorvl) phenylacetate 0. 2 0.0009 0.055 0.0004 0. 25 3 Ethyl alpha-(0,0-diethyldlth1 phoryl)4-ehlorophenyl acetate 0. 22 0. 0014 0. 16 0.00065 0. 1 5

I 7 7 We claim;

1'. In-tljie artfof controlling pests of the group consisting of flies, aphides, mites, and fungi the improvement comprising applying to the locality frequented by the pest an 0,0-dialkyl-dithiophosphoric acid ester of the formula RO\ Si ,4 2 RO- S-CH-COOR 3. In the art of controlling pests of the group consisting of flies, aphides, mites; and fungi, the improvement comprising applying to the locality frequentedbythe pest the' isopropyl ester of' alpha(O,O-diethyldithiophosphoryl) phenylacetic acid. r

4: Thepesticidal compound, the etl iyl" ester of alpl1a- (0,0-diethyldithiophosphoryl) -p-nitrophenyl'aceticacid.

5. The pesticidal compound, the ethyl ester of alpha (0,0 diethyldithiophosphoryl)-p-chlorophenylacetic acid.

References; Cited in the file of this patent UNITED STATES PATENTS 2,266,514 Romieux et al Dec. 16, 1941 2,494,283 Cassaday et al Jan.-10, 1950 2,494,284 Cassaday et a1 Jan. 10, 1950 2,645,657 Rudel et a1. July 14,1953

OTHER REFERENCES Gar et al.; Doklady Akadl Nauk S.S.S;R.," 94, 2411-4 (In Russian.) Chem. Abst., 48, 6639-40, 1954. 

1. IN THE ART OF CONTROLLING PESTS OF THE GROUP CONSISTING OF FLIES, APHIDES, MITES, AND FUNGI, THE IMPROVEMENT COMPRISING APPLYING TO THE LOCALITY FREQUENTED BY THE PEST AN 0,0-DIALKYL-DITHIOPHOSPHORIC ACID ESTER OF THE FORMULA
 5. THE PESTICIDAL COMPOUND, THE ETHYL ESTER OF ALPHA(0,0-DIETHYLDITHIOPHOSPHORYL)-P-CHLOROPHENYLACETIC ACID. 